Flotation of aluminosilicate, phosphate and fluoride ores

ABSTRACT

Mineral concentrates are obtained from aluminosilicate and alkali and alkaline earth aluminosilicate, phosphate and fluoride ores in a beneficiation process in which the ore is conditioned prior to flotation with a C20 to C22 saturated or unsaturated fatty acid or a mixture of C20 to C22 saturated or unsaturated fatty acids and C18 or lower fatty acids and an alicyclic or aromatic hydrocarbon oil.

United States Patent 1 Knocke et a1.

1 1 Jan.7, 1975 1 FLOTATION OF ALUMINOSILICATE,

PHOSPHATE AND FLUORIDE ORES [75] Inventors: Louis C. Knocke, Shelby, NC;

William Novis Smith, Jr., Chester, Pa.

[52] U.S. C1. 209/166 [51] Int. Cl 803d 1/02 [58] Field of Search 209/166, 167

[56] References Cited UNITED STATES PATENTS 1,912,433 6/1933 Crago 209/166 2,084,413 6/1937 Siems 209/166 2,748,938 6/1956 Bunge 209/166 3,028,008 4/1962 Browning 209/167 3,032,196 5/1962 Sollin 209/166 3,078,997 2/1963 Mavens 209/167 X 3,278,028 10/1966 Miusaps 209/166 3,295,767 l/l967 Becker 209/166 3,353,672 11/1967 SOllin .l 209/166 3,430,765 3/1969 Allen 209/166 X 3,459,299 8/1969 Mercade 209/166 X OTHER PUBLICATIONS Chem. Abst., Vol. 71, 1969, 633 30u. Chem. Abst., Vol. 73, 1971, 1l2000p.

Primary ExaminerRobert Halper Attorney, Agent, or Firm-Howson and Howson 57 ABSTRACT Mineral concentrates are obtained from aluminosilicate and alkali and alkaline earth aluminosilicate, phosphate and fluoride ores in a beneficiation process in which the ore is conditioned prior to flotation with a C to C saturated or unsaturated fatty acid or a mixture of C to C saturated or unsaturated fatty acids and C or lower fatty acids and an alicyclic or aromatic hydrocarbon oil.

9 Claims, N0 Drawings FLOTATION OF ALUMINOSILICATE, PHOSPHATE AND FLUORIDE ORES BACKGROUND OF THE INVENTION This invention relates to a beneficiation process in which minerals are concentrated by froth flotation utilizing a C to C saturated or unsaturated fatty acid or a mixture of C to C saturated or unsaturated fatty acids and C or lower fatty acids and an alicyclic or aromatic hydrocarbon oil to condition the ore prior to flotation.

It is widely recognized that saturated and unsaturated fatty acids may be utilized in beneficiation processes to condition an ore pulp prior to flotation. For example, U.S. Pat. No. 3,028,008 describes a beneficiation process in which spodumene is isolated from mineral mixtures containing spodumene and beryllium. This process includes a flotation step which utilizes multicomponent collecting aids consisting of magnesium based lignin sulfonate, sodium fluoride and a fatty acid such as oleic acid to condition the mineral mixture prior to flotation. U.S. Pat. No. 3,329,265 describes a process for the beneficiation of mica ores by flotation which utilizes a combination of a cationic and an anionic reagent as flotation collecting aids, suitable anionic reagents being described as saturated or unsaturated fatty acids containing 8 to 20 carbon atoms or salts thereof. U.S. Pat. No. 3,278,028 also describes a beneficiation process utilizing saturated and unsaturated fatty acids containing 8 to 20 carbon atoms or salts thereof as collecting aids for the flotation of mica ores. U.S. Pat. No. 2,974,884 describes a beneficiation process for recovering lithium from lithium aluminosilicate ores utilizing tall oil fatty acids and methyl isobutylcarbinol to condition the ore prior to flotation.

U.S. Pat. No. 1,902,839 discloses a froth flotation process in which a mixture of a fatty acid, such as oleic acid and a hydrocarbonaceous thiophosphoric acid compound is utilized as a collecting aid. U.S. Pat. No. 3,061,097 describes a flotation process for separating carbonaceous materials such as kerogen and paraffin from oil shales which utilizes monocyclic hydrocarbons as collecting aids.

It is the object of this invention to provide collecting aids useful in conditioning ores prior to froth flotation in a beneficiation process which produces mineral concentrates from aluminosilicate and alkali and alkaline earth metal aluminosilicate, phosphate and fluoride ores.

DETAILED DESCRIPTION OF THE INVENTION This invention relates to a beneficiation process which utilizes a froth flotation procedure in which an ore is conditioned prior to flotation with from about 0.25 to about 4 lbs. per ton of ore of a fatty acid collecting aid, said fatty acid being selected from the group consisting of a fatty acid containing 20 to 22 carbon atoms and a mixture of fatty acids containing from about to about 75% of a fatty acid containing to 22 carbon atoms, the balance C or lower fatty acids, said percentages being by weight, based on the weight of the fatty acid mixture and from about 0.05 to about 1 lb. per ton of ore of an alicyclic or aromatic hydrocarbon oil selected from the group consisting of turpentine, pinene, mesitylene, cedrene and 1,3- dicyclopentadiene to provide a mineral concentrate from an ore selected from the group consisting of aluminosilicate and alkali and alkaline earth metal aluminosilicate, phosphate and fluoride ores.

It has now been found that a combination of fatty acids having 20 to 22 carbon atoms per molecule or mixtures of C to C fatty acids with C or lower fatty acids and an alicyclic or aromatic hydrocarbon oil acts as an extremely efficient collecting aid when utilized to condition aluminosilicate, and alkali and alkaline earth metal aluminosilicate, phosphate and fluoride ores prior to froth flotation. The C to C fatty acids utilized as the fatty acid component of the collecting aid in this process include both saturated and unsaturated fatty acids such as erucic, arachidic, n-heneicosoic, behenic, gadoleic, cetoleic and brassidic acids, erucic acid being especially preferred. As will be recognized, mixtures of two or more of these acids in any proportions may be utilized in the collecting aids in this invention, although, commonly a single acid will be utilized.

Certain mixtures of the C to C fatty acids with C or lower fatty acids, particularly those mixtures containing from about 15 to about of a fatty acid containing 20 to 22 carbon atoms, balance C or lower fatty acids, said percentages being by weight, based on the weight of the fatty acid mixture have also been found useful as collecting aids when combined with an alicyclic or aromatic hydrocarbon oil. Useful C or lower fatty acids which may be utilized in forming the collecting aids include tall oil fatty acids, oleic acid, stearic acid, palmitic acid and the like. When desirous of using a mixture of C to C fatty acids with C or lower fatty acids, the fatty acids may be combined in any conventional manner such as by mixing until a uniform product is obtained.

In addition to the fatty acid component, the collecting aid of this invention includes an alicyclic or aromatic hydrocarbon oil. Useful alicyclic or aromatic hydrocarbon oils which are to be combined with the fatty acid component of the collecting aid include turpentine, pinene, mesitylene, cedrene and 1,3- dicyclopentadiene.

In general, the beneficiation process of this invention includes a conventional froth flotation procedure in which an ore is first ground to a reduced particle size and introduced into a flotation cell where the collecting aids of this invention are added to treat the ore prior to introduction of air into the flotation cell. While not always required, certain ores may be deslimed after the grinding procedure, the pulp recovered from the desliming operation being passed to the flotation cell for treatment with the collecting aid.

The ground ore is introduced into the flotation cell in the form of a slurry, the slurry containing the ore particles at levels ranging from about 5 to about 40% solids. The collecting aid is combined with the ore slurry in the flotation cell in a proportion of from about 0.25 to about 4 lbs. per ton of ore (based on the ore in the slurry) of the fatty acid components and from about 0.05 to about 1 lb. per ton of ore (based on the ore in the slurry) of the alicyclic or aromatic hydrocarbon oil component of the collecting aid. The fatty acid component and the hydrocarbon oil component of the collecting aid may be added to the flotation cell simultaneously, or they may be added individually in any sequence desired so long as both components are present in the flotation cell and are allowed to condition the ore prior to introduction of air into the cell.

The ore is conditioned with the collecting aid for a period of time ranging from a few minutes up to as long as an hour. No special conditions are required for the conditioning, however, should it'be desired, the ore and collecting aid may be heated to temperatures up to as high as 100C. during the conditioning period. Optimum quantities of the collecting aid, length of conditioning and other parameters of the conditioning process are best determined empirically and will vary considerably depending on the type and amount of ore treated as well as the type of mineral concentrate desired. Combination fatty acid alicyclic or aromatic hydrocarbon oil collecting aids have been found to be especially useful in a beneficiation process designed to recover ceramic grade spodumene, spodumene containing not less than 6.6% Li O and less than 0.9% F6203 from lithium aluminosilicate ores. In this process, the lithium aluminosilicate ore is ground, de-

slimed and transferred in a slurry containing from 5 to in a hydrocyclone, conditioned with a collection aid for minutes and fed in the form ofa slurry of about solids into a flotation cell where the desired components of the ore were isolated and recovered in the froth formed with the introduction of air into the flotation cell. In Table I which follows below, the ore samples subjected to froth flotation are characterized by the particle size and the U 0 content of the ore, this characterization being found in the columns headed Feed in Table I. The collecting aid utilized to treat the ore slurry prior to flotation, is a mixture of erucic acid and tall oil fatty acid with various alicyclic or aromatic hydrocarbon oils, the flotation collecting aid being combined with-the ore in a proportion of 0.45 lbs. of erucic acid per ton of ore, 0.33 lbs. of tall oil per ton of ore and 0.11 lbs. of oil per ton of ore, all based on the ore in the feed slurry. The spodumene recovered in this manner is characterized in Table I in the columns enumerating the weight recovery of spodumene, the weight of spodumene recovered in terms of Li O, the purity of the spodumene recovered expressed in terms of Li O and the weight recovery of spodumene expressed as percent recovery of available mesh spodumene. For sake of comparison, one test was run containing no oil in the collecting aid.

TABLE I VARIOUS OILS AS FLOTATION COLLECTION AIDS WITH HIGH CHAIN FATTY ACIDS Collecting Aid Feed Recovery Sample Oil Fatty Wt. %Li O Spodumene of Available No. Compon- Acid Li O +50 Recov-' Re- Concentrate +50 Mesh ent* Component Mesh cred covered Lao Spodumene I None 3.11 10 18.9 73.2 6.34 62.1 2 Pinene 3.11 10 22.2 80.7 6.06 88.3 3 Mesitylene 3.11 10 17.4 74.5 6.78 52.8 4 Dicyclopentadiene 3.11 10 22.6 83.7 6.01 84.9 5 Cedrene 3.11 10 29.3 88.3 5.03 81.6

0.11 lbs. per ton ore feed "FATTY ACID COMPONENT: a mixture of0.45 lbs. per ton ore feed of erucic acid and 0.33 lbs. per ton ore feed of tall oil fatty acids 35% solids slurry carbon oil, followed by introduction of air into the cell which causes the particles of the desired spodumene to float to the surface of the cell in the form of a froth which is collected and further treated to recover the desired ceramic grade spodumene.

Beneficiation process including a flotation procedure which utilizes the collecting aids described herein have been found to be particularly desirable, resulting in the recovery of a spodumene concentrate in which the predominant portion at least 75%, or more, by weight, based on the weight of the concentrate recovered, is ceramic grade spodumene containing not less than about 6.6% U 0 and less than about 0.9% Fe O The collecting aids of this invention have been found to promote the flotation of relatively large, 28 to 48 mesh, mineral particles, a significant factor contributing to the enhanced recovery of ceramic grade spodumene just described.

The invention will be illustrated by the following example.

EXAMPLE 1 A series of lithium aluminosilicate ore samples were ground to a particle size of 28 mesh by down, deslimed Having thus described the invention, What is claimed 1. In a beneficiation process including froth flotation of ground ore to provide a mineral concentrate from an ore selected from the group consisting of aluminosilicate and alkali and alkaline earth metal aluminosilicate, phosphate and fluoride ores, the improvement consisting essentially of conditioning the ground ore prior to flotation with from about 0.25 to about 4 lbs. per ton of ore based on the ore being treated, of a fatty acid collecting aid said fatty acid being selected from the group consisting of a fatty acid containing 20 to 22 carbon atoms and a mixture of fatty acids containing from about 15 to about of a fatty acid containing 20 to 22 carbon atoms, balance C or lower fatty acids, said percentage being by weight, based on the weight of the fatty acid mixture and from about 0.05 to about 1 lb. per ton of ore,'based on the ore being treated of an alicyclic or aromatic hydrocarbon oil selected from the group consisting of turpentine, pinene, mesitylene, cedrene and 1,3-dicyclopentadiene.

2. The process of claim 1 wherein said fatty acid component of the collecting aid is a fatty acid containing 20 to 22 carbon atoms said fatty acid being a member of the group consisting of saturated fatty acids, unsaturated fatty acids or mixtures of saturated and unsaturated fatty acids in any proportion.

3. The process of claim 2 wherein said fatty acid is erucic acid.

4. The process of claim 1 wherein said fatty acid component of the collecting aid is a mixture of fatty acids containing from about'l5% to about 75% of a fatty acid containing 20 to 22 carbon atoms, balance C or lower fatty acids, said percentage being by weight based on the weight of the fatty acid mixture.

5. In a beneficiation process including froth flotation of ground lithium aluminosilicate ores to provide a lithium aluminosilicate mineral concentrate, the improvement comprising conditioning the ground ore prior to flotation with from about 0.25 to about 4 lbs. per ton of ore based on the ore being treated, of a fatty acid collecting aid said fatty acid being selected from the group consisting of a fatty acid containing 20 to 22 carbon atoms and a mixture of fatty acids containing from about to about 75% of a fatty acid containing to 22 carbon atoms, balance C or lower fatty acids, said percentage being by weight based on the weight of the fatty acid mixture and from about 0.05 to about l lb.

per ton of ore, based on the ore being treated, of an alicyclic or aromatic hydrocarbon oil selected from the group consisting of turpentine, pinene, mesitylene,'cedrene and l,3-dicyclopentadiene.

6. The process of claim 5 wherein said fatty acid component of the collecting aid is a fatty acid containing 20 to 22 carbon atoms said fatty acid being a member of the group consisting of saturated fatty acids, un-

saturated fatty acids or mixtures of saturated and unsaturated fatty acids in any proportion.

7. The process of claim 5 wherein said fatty acid is erucic acid.

mene. 

1. IN A BENEFICIATION PROCESS INCLUDING FROTH FLOTATION OF GROUND ORE TO PROVIDE A MINERAL CONCENTRATE FROM AN ORE SELECTED FROM THE GROUP CONSISTING OF ALUMINOSILICATE AND ALKALI AND ALKALINE EARTH METAL ALUMINOSILICATE, PHOSPHATE AND FLUORIDE ORES, THE IMPROVEMENT CONSISTING ESSENTIALLY OF CONDITIONING THE GROUND ORE PRIOR TO FLOTATION WITH FROM ABOUT 0.25 TO ABOUT 4 LBS. PER TON OF ORE BASED ON THE ORE BEING TREATED, OF A FATTY ACID COLLECTING AID SAID FATTY ACID BEING SELECTED FROM THE GROUP CONSISTING OF A FATTY ACID CONTAINING 20 TO 22 CARBON ATOMS AND A MIXTURE OF FATTY ACIDS CONTAINING FROM ABOUT 15 TO ABOUT 75% OF A FATTY ACID CONTAINING 20 TO 22 CARBON ATOMS, BALANCE C18, OR LOWER FATTY ACIDS, SAID PERCENTAGE BEING BY WEIGHT, BASED ON THE WEIGHT OF THE FATTY ACID MIXTURE AND FROM ABOUT 0.05 TO ABOUT 1 LB. PER TON OF ORE, BASED ON THE ORE BEING TREATED OF AN ALICYCLIC OR AROMATIC HYDROCARBON OIL SELECTED FROM THE GROUP CONSISTING OF TURPENTINE, PINENE, MESITYLENE, CEDRENE AND 1,3-DICYCLOPENTADIENE.
 2. The process of claim 1 wherein said fatty acid component of the collecting aid is a fatty acid containing 20 to 22 carbon atoms said fatty acid being a member of the group consisting of saturated fatty acids, unsaturated fatty acids or mixtures of saturated and unsaturated fatty acids in any proportion.
 3. The process of claim 2 wherein said fatty acid is erucic acid.
 4. The process of claim 1 wherein said fatty acid component of the collecting aid is a mixture of fatty acids containing from about 15% to about 75% of a fatty acid containing 20 to 22 carbon atoms, balance C18 or lower fatty acids, said percentage being by weight based on the weight of the fatty acid mixture.
 5. In a beneficiation process including froth flotation of ground lithium aluminosilicate ores to provide a lithium aluminosilicate mineral concentrate, the improvement comprising conditioning the ground ore prior to flotation with from about 0.25 to about 4 lbs. per ton of ore based on the ore being treated, of a fatty acid collecting aid said fatty acid being selected from the group consisting of a fatty acid containing 20 to 22 carbon atoms and a mixture of fatty acids containing from about 15 to about 75% of a fatty acid containing 20 to 22 carbon atoms, balance C18 or lower fatty acids, said percentage being by weight based on the weight of the fatty acid mixture and from about 0.05 to about 1 lb. per ton of ore, based on the ore being treated, of an alicyclic or aromatic hydrocarbon oil selected from the group consisting of turpentine, pinene, mesitylene, cedrene and 1,3-dicyclopentadiene.
 6. The process of claim 5 wherein said fatty acid component of the collecting aid is a fatty acid containing 20 to 22 carbon atoms said fatty acid being a member of the group consisting of saturated fatty acids, unsaturated fatty acids or mixtures of saturated and unsaturated fatty acids in any proportion.
 7. The process of claim 5 wherein said fatty acid is erucic acid.
 8. The process of claim 5 wherein said fatty acid component of the collecting aid is a mixture of fatty acids containing from about 15% to about 75% of a fatty acid containing 20 to 22 carbon atoms, balance C18 or lower fatty acids, said percentages being by weight based on the weight of the fatty acid mixture.
 9. The process of claim 5 wherein the lithium aluminosilicate mineral recovered is ceramic grade spodumene. 